Blends of poly[α-methylenelact(one)(am] homo- and copolymers

ABSTRACT

Polymers containing α-methylenelact(ones)(ams) such as α-methylenebutyrolactones are useful in blends with other polymers. For examples such polymers which have reactive groups are toughened by mixing with a rubbery material which has complimentary reactive groups, or polymers containing repeat units derived from α-methylenelact(ones)(ams) are toughened by mixing with polymeric core-shell particles having an elastomeric core and a specified thermoplastic shell. The properties of thermoplastics are also improved by blending with α-methylenelact(ones)(ams) such as α-methylenebutyrolactones containing (co)polymers.

FIELD OF THE INVENTION

Polymers containing repeat units derived from α-methylenelact(ones)(ams)such as α-methylenebutyrolactones and which have reactive groups aretoughened by mixing with a rubbery material which has complimentaryreactive groups, or polymers containing repeat units derived fromα-methylenelact(ones)(ams) are toughened by mixing with polymericcore-shell particles having an elastomeric core and a specifiedthermoplastic shell; or blends of polymers containing repeat unitsderived from α-methylenelact(ones)(ams) with thermoplastics often yieldcompositions which have a higher modulus and/or heat deflectiontemperature than the thermoplastic alone.

TECHNICAL BACKGROUND

Thermoplastics comprise a large body of commercially important products.Among the uses of thermoplastics are those in which the opticalproperties of the polymer are important, particularly when the polymeris an optically clear material with little distortion of optical images.Such polymers, for example poly(methyl methacrylate) (PMMA) and certainpolycarbonates are used as substitutes for glass where toughness isimportant. In uses such as for safety glazing and signage, otherproperties such as weather and/or heat resistance may also be important.For example if such a part needed to be thermally sterilized, it mustwithstand the temperature of the sterilization process. Polycarbonatesoften have poor weathering and/or hydrolysis resistance, while PMMA hasa relatively low glass transition temperature (Tg), so its heatresistance is poor. Thus polymers with a combination of good opticalproperties, and heat and weathering resistance are desired.

The polymers of certain α-methylenelact(ones)(ams) (AMLs) have thecombination of good properties, but often are quite brittle, see forinstance U.S. Pat. No. 5,880,235, and the discussion at columns 1-3, andD. Arnoldi, et al., Kunststoffe, vol. 87, p. 734-736 (1997). Thus if onecould toughen these polymers without compromising their other superiorproperties, useful compositions would result.

While the toughening of AMLs using toughening agents is in theApplicant's knowledge not reported in the literature, toughening ofthermoplastics in general using toughening agents is known. For example,poly(meth)acrylates have been toughened by a number of methods, see forinstance U.S. Pat. Nos. 5,625,001 and 5,998,554, and World PatentApplication 99/12986.

Tougheners for various types of engineering resins [including(meth)acrylics] and other polymers are sold by Rohm and Haas Co.,Philadelphia, Pa, U.S.A. under the tradename Paraloid®, such as theirEXL™ series which is believe to be a core-shell polymeric particleproduct with a rubber core and thermoplastic shell, and also see forinstance U.S. Pat. Nos. 3,678,133, 3,793,402, 3,808,180, 3,985,703,4,180,494, and 4,543,383.

Other types of thermoplastics have been toughened by the addition ofelastomeric polymers which contain reactive groups such as epoxides, seefor instance U.S. Pat. No. 4,753,980.

Conversely, AMLs may be used to improve the properties ofthermoplastics, including thermoplastics containing functional groupswhich potentially may react with the AML. Such thermoplastics includepolyamides, polyesters, and polyacetals, and nonfunctional groupcontaining thermoplastics such as styrene/acrylonitrile copolymers. Itis believed that to be most effective in improving properties, the AMLshould be dispersed within a matrix of the thermoplastic.Polymer-polymer blends of various polymers are well known in the art,but to Applicants' knowledge, no blends of AMLs with other polymers havebeen reported.

SUMMARY OF THE INVENTION

This invention concerns a first composition, comprising:

(a) a first polymer comprising the repeat units:

(i) at least about 10 mole percent of the total repeat units of

(ii) at least about 0.1 mole percent of a repeat unit containing a firstreactive functional group;

(iii) up to about 89.9 mole percent of repeat units derived from one ormore monomers which are free radically copolymerizable with (a)(i) and(a)(ii); and

(b) about 1 weight percent to about 50 weight percent based on the totalweight of (a) and (b), of a second polymer which is elastomeric andcontains a second reactive functional group which may react with saidfirst reactive functional group;

or

(c) a third polymer comprising the repeat units

(i) at least about 10 mole percent of the total repeat units of

(ii) up to about 90 mole percent of repeat units derived from one ormore monomers which are free radically copolymerizable with (b)(i); and

(d) about 1 percent by weight to about 60 percent by weight based on thetotal weight of (c) and (d), of a fourth polymer which is core-shellparticles made up of an elastomeric polymer core and a polymericthermoplastic shell, said thermoplastic shell comprising repeat unitsderived from methyl methacrylate

wherein:

n is 0, 1 or 2;

X is —O— or —NR⁹—; and

R¹, R², R⁵, R⁶, each of R³, and each R⁴, are independently hydrogen, afunctional group, hydrocarbyl or substituted hydrocarbyl; and

R⁹ is hydrogen, hydrocarbyl or substituted hydrocarbyl.

This invention also concerns a second composition, comprising:

(e) a fifth polymer comprising the repeat units:

(i) at least about 10 mole percent of the total repeat units of

(ii) optionally a repeat unit containing a third reactive functionalgroup;

(iii) up to about 90 mole percent of repeat units derived from one ormore monomers which are free radically copolymerizable with (e)(i), and(e)(ii), if present; and

(f) a sixth polymer which is a thermoplastic and which may optionallycontain one or more fourth reactive functional groups which may reactwith said third functional group;

provided that in said composition (b) is present as a continuous orcocontinuous phase and (a) is present as a dispersed or cocontinuousphase;

and wherein:

n is 0, 1 or 2;

X is —O— or —NR⁹—; and

R¹, R², R⁵, R⁶, each of R³, and each R⁴, are independently hydrogen, afunctional group, hydrocarbyl or substituted hydrocarbyl; and

R⁹ is hydrogen, hydrocarbyl or substituted hydrocarbyl.

DETAILS OF THE INVENTION

Certain terms are used herein as defined below.

By “hydrocarbyl group” is meant a univalent group containing only carbonand hydrogen. If not otherwise stated, it is preferred that hydrocarbylgroups (and alkyl groups) herein contain 1 to about 30 carbon atoms.

By “substituted hydrocarbyl” is meant a hydrocarbyl group which containsone or more substituent groups which are inert under the processconditions to which the compound containing these groups is subjected.The substituent groups also do not substantially interfere with theprocess. If not otherwise stated, it is preferred that substitutedhydrocarbyl groups herein contain 1 to about 30 carbon atoms. Includedin the meaning of “substituted” are heteroaromatic rings. In substitutedhydrocarbyl all of the hydrogens may be substituted, as intrifluoromethyl.

By “functional group” is meant a group other than hydrocarbyl orsubstituted hydrocarbyl which is inert under the process conditions towhich the compound or polymer containing the group is subjected. Thefunctional groups also do not substantially interfere with any processdescribed herein that the compound or polymer in which they are presentmay take part in. Examples of functional groups include halo (fluoro,chloro, bromo and iodo), ether such as —OR²² wherein R²² is hydrocarbylor substituted hydrocarbyl.

By “reactive functional group” is meant a functional group that mayreact with another functional group present in the process orcomposition. By “may react” is meant that the functional group may reactwith its counterpart reactive group, but it is not necessary that suchreaction happen or that all of the reactive functional groups react withone another. Usually in the formation of the compositions describedherein some fraction of these reactive functional groups will react.

By “copolymerizable under free radical conditions” is meant that the(potential) monomers, preferably vinyl monomers, involved are known tocopolymerize under free radical polymerization conditions. The freeradicals may be generated by any of the usual processes, for examplethermally from radical initiators such as peroxides or azonitriles, byUV radiation using appropriate sensitizers, and by ionizing radiation.The copolymerization may be done in any number of known ways, forexample bulk, solution, suspension, or aqueous suspension or emulsion,or combinations of methods such as bulk-suspension. These polymers maybe prepared by various types of processes, such as continuous, batch andsemibatch, which are well known in the art. Many combinations of freeradically copolymerizable monomers are known, see for instance J.Brandrup, et al., Ed., Polymer Handbook, 4^(th) Ed., John Wiley & Sons,New York, 1999, p. II/181-II/308.

By “elastomeric or rubbery polymer” is meant a polymer having a flexuralmodulus (of unfilled pure elastomeric polymer) of 35 MPa or less whenmeasured by ASTM D790, and not having a Tg above 30° C., preferably nothaving a Tg above 0° C. Glass transition temperatures are measured byASTM D3418 at a heating rate of 20° C./min and the Tg is taken as themidpoint of the transition.

In the first, third and fifth polymers herein, (I) is present as arepeat unit. (I) is derived from the monomer

wherein X and R¹ through R⁶ and R⁹ are as defined above. In preferredstructures (I) and (III):

n is 0; and/or

R¹, R², R³, R⁴, R⁵ and R⁶ are hydrogen or alkyl containing 1 to 6 carbonatoms, more preferably all are hydrogen; and/or

X is —O— or —NR⁹— wherein R⁹ is hydrogen or alkyl containing 1 to 6carbon atoms, more preferably X is —O—.

In particularly preferred structures for (I) and (III), n is 0, X is —O—and R¹, R², R⁵ and R⁶ are hydrogen, or n is 0, X is —O—, R⁶ is methyl,and R¹, R² and R⁵ are hydrogen. For other preferred structures of (I)and (III) see U.S. Pat. No. 5,880,235, which is hereby included byreference, at column 4, line 44 to column 8, line 59.

In the first polymer (I) is at least about 10 mole percent of the repeatunits present, preferably at least about 20 mole percent, morepreferably at least about 50 mole percent. The repeat unit (a)(ii) inthe first polymer has a functional group which is reactive (with afunctional group in the second polymer). Useful functional groups inrepeat unit (a)(ii) are epoxy, carboxylic anhydride, isocyanato,hydroxyl, carboxyl, and primary and secondary amino. Repeat unitscontaining these functional groups may be derived from maleic acid oranhydride (for carboxylic anhydride) or from functional (meth)acrylatesof the formula

wherein R¹³ is hydrogen or methyl and Z may be (for example) —OH,—OCH₂CH₂OH, —N(CH₃)CH₂CH₂NH₂, and

In a preferred repeat unit (a)(ii) Z is —OH (acrylic or methacrylicacid) and it is even more preferred if R¹³ is methyl (methacrylic acid).Preferably the level of repeat unit (a)(ii) is about 0.1 to about 25mole percent, more preferably about 1 to about 10 mole percent, of thetotal repeat units. In another preferred repeat unit (a)(ii) Z is—CH₂CH₂OH (2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate), morepreferably in this compound R¹³ is methyl (2-hydroxyethyl methacrylate).

In the fifth polymer a repeat unit (e)(ii) containing a third reactivefunctional group may be present. This repeat unit may be derived frommonomers listed above for repeat unit (a)(ii), and be present at thesame levels preferred for (a)(ii). It is also to be noted that in thefifth polymer it is possible that repeat units derived from (I) may alsoreact with the fourth functional group. These are not considered to berepeat unit of the type (e)(ii) but of type (e)(i). For example thelactone ring of a (e)(i) may open and react with a functional group of(e)(iii).

In the first, third and fifth polymers additional repeat units (a)(iii),(c)(ii), and (e)(iii), respectively, may also be present. Preferablythese repeat units have the formula

wherein R¹⁴ is hydrogen or methyl, and R¹⁵ is hydrocarbyl or substitutedhydrocarbyl, preferably alkyl, and R¹⁶ is hydrogen or methyl and R¹⁷,R¹⁸, R¹⁹, R²⁰ and R²¹ are each independently hydrogen, hydrocarbylsubstituted hydrocarbyl or a functional group. In a preferred structure(V) R¹⁴ and R¹⁵ are both methyl (methyl methacrylate), and in apreferred structure (VI) R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ are allhydrogen (styrene).

In a particularly preferred first or fifth polymer, 0 to about 40 molepercent of the repeat units present are derived from methylmethacrylate, and 0 to about 5 mole percent of the repeat units arederived from an alkyl acrylate wherein the alkyl group has 2-4 carbonatoms, more preferably ethyl acrylate or n-butyl acrylate. In aparticularly preferred third polymer, 0 to about 40 mole percent of therepeat units present are derived from methyl methacrylate, and 0 toabout 5 mole percent of the repeat units are derived from an alkylacrylate wherein the alkyl group has 2-4 carbon atoms, more preferablyethyl acrylate or n-butyl acrylate. The second polymer is elastomeric,or a core-shell polymer wherein the second reactive functional group isin the shell portion of the polymer, and amount of functional asdescribed below refer to the amount of second functional group in thecore portion of the core-shell polymer only. The core-shell polymers aresimilar to those described below for the fourth polymer, except have afunctional group in the shell. Such functional groups may beincorporated for example by copolymerizing a functional monomer such asa hydroxyethyl (meth)acrylate or glycidyl (meth) acrylate into theshell. Preferably the shell of this core-shell polymer also comprisesrepeat units derived from methyl methacrylate.

Generally speaking the first, third and fifth polymers may be mixed inany proportion with one or more other type(s) of polymer(s) to form apolymer blend. The other polymer(s) may be an elastomer (with or withoutfunctional groups), and/or a thermoplastic. The elastomer may or may notbe crosslinked. It is preferred that in such blends there be acontinuous phase and a dispersed phase. Depending on the composition ofthe blend and its desired properties, the first third or fifth polymersmay be the dispersed or continuous phases, and the other polymer(s)present would be in the complementary phase. Preferably the first thirdand fifth polymers are 1 to 99 volume percent of the blend and the otherpolymer(s) are 99 to 1 volume percent of the blend. Preferred firstthird and fifth polymers for these general types of blends are the sameas described above for the first third and fifth polymers.

The second polymer has a second reactive functional group which mayreact with the first reactive functional group of the first polymer.Table 1 below gives some useful functional groups and some of thecorresponding functional groups with which they may react. Eitherfunctional group of these reactive pairs may be present in the firstpolymer and the other functional group present in second polymer.

TABLE 1 Functional Group Complimentary Functional Group carboxyl amino,hydroxyl epoxy hydroxyl, amino, carboxyl carboxylic anhydride hydroxyl,amino isocyanato hydroxyl, amino, carboxyl

In one particularly preferred combination of first and second polymersthe first polymer contains carboxyl or hydroxyl groups, especiallypreferably derived from methacrylic acid, in the case of carboxylgroups, and from a hydroxyalkyl (meth)acrylate, especially2-hydroxyethyl methacrylate, in the case of hydroxy groups, and thesecond polymer contains epoxy groups. A particularly preferred secondpolymer is an elastomeric copolymer of ethylene, an alkyl (particularlythose having 1-8 carbon atoms) acrylate and glycidyl acrylate ormethacrylate, particularly glycidyl methacrylate. Such copolymers aredescribed in U.S. Pat. No. 4,753,980, which is hereby included byreference. For example such a copolymer may contain 40-90 weight percentethylene repeat units, 10-40 weight percent of an alkyl acrylate ormethacrylate, and 0.5-20 weight percent of glycidyl acrylate ormethacrylate. Another type of second polymer which is useful is anelastomeric polymer on which a compound containing an appropriatefunctional group has been grafted, for example an ethylene/propylene(EP) or ethylene/propylene/diene (EPDM) rubber grafted with maleicanhydride. Preferably the second polymer contains about 0.01 to about1.5 moles, more preferably about 0.03 moles to about 1.0 moles of thesecond reactive group per kg of second polymer.

The fourth polymer is in the form of so-called core-shell particles.These are polymer particles, often made in suspension or emulsionpolymerization, which have a core of one polymer, and a shell (outerlayer) of another polymer. These polymers are well known, and known tobe useful for the toughening of various thermoplastics, see for instanceU.S. Pat. Nos. 3,678,133, 3,793,402, 3,808,180, 3,985,703, 4,180,494,and 4,543,383, all of which are hereby included by reference. For theelastomeric core various types of elastomers may be used, for examplepoly-1,3-butadiene, poly(meth)acrylic esters and their variouscopolymers, EPDM, and other polymers. Preferred core materials arepoly(1,3-butadiene-co-styrene), and various elastomeric acrylatecopolymers, for example those containing one or more of ethyl acrylate,n-butyl acrylate, and 2-ethylhexyl acrylate. For the thermoplastic shellvarious (meth)acrylic polymers may be used, but poly(meth)acrylic estersand their copolymers are preferred. A preferred shell material is PMMAor a copolymer of methyl methacrylate which is at least 50 weightpercent methyl methacrylate. The core and/or shell may be crosslinked invarious ways, for example by using difunctional monomers in relativelysmall amounts to form crosslinks. It is preferred that the shell portionof the particle be relatively thin, so that at least about 50 percent byvolume of the average particle is elastomeric (core) polymer.

The sixth polymer may have fourth functional groups which arecomplimentary to the third reactive functional groups, in an analogousmanner to the first and second reactive functional groups above.

Polymers containing (I) may be made by the free radical(co)polymerization of (III), see for instance U.S. Pat. No. 5,880,235and references cited therein. When (I) is present in a copolymer, ittends to raise the Tg of most copolymers. For example in a copolymer of(III) with methyl methacrylate, the Tg will normally be above the Tg ofa PMMA homopolymer.

In the first composition some of the toughened polymers described hereinare transparent when visually viewed, see for instance Examples 2 and 5.It is believed the toughening agents used in these examples haverefractive indices very close to the polymer being toughened.

When the two (or more) polymers of the first composition are mixed, itis preferred that the second polymer be uniformly dispersed in the firstpolymer, or the fourth polymer be uniformly dispersed in the thirdpolymer. It is preferred that the discontinuous phase (second or fourthpolymers) be of relatively small particle size, typically in the rangeof 0.01-10 μm. This can be achieved in high shear melt mixers such assingle and especially twin-screw extruders, or other types of meltmixers.

In the second composition herein a sixth polymer, a thermoplastic, ispresent in a blend with a fifth polymer, which is a homo- or copolymerof (I), preferably a copolymer of (I). By “thermoplastic” is meant theusual meaning, a polymer which contains crystallites at 30° C. whichhave a heat of fusion of 1 J/g or more, or whose glass transitiontemperature is greater than 30° C. when measured by ASTM D3418 at aheating rate of 20° C./min and the Tg is taken as the midpoint of thetransition. Useful thermoplastics include polyesters such aspoly(ethylene terephthalate) and poly(butylene terephthalate),polyamides such as nylon-6,6 and nylon-6, polyolefins such aspolyethylene and polypropylene, liquid crystalline polymers includingpolyesters and poly(ester-amides), other vinyl addition polymers such aspolystyrene and poly(styrene-co-acrylonitrile), polyacetals,polycarbonates and poly(meth)acrylates such as poly(methylmethacrylate). Preferred sixth polymers are polyamides, especiallynylon-6 and nylon-6,6, polyester, especially poly(ethyleneterephthalate) and poly(butylene terephthalate), and polyacetalsespecially polyoxymethylene. In the second composition the fifth polymeris preferably present as dispersed particles. The sixth polymer ispreferably present as a continuous phase. This phase relationship ismost readily obtained when the major portion of the polymer blend byvolume is the sixth polymer and the minor portion is the fifth polymer(based on the total volume of fifth and sixth polymers present).Preferably the fifth polymer is about 5 to about 70 weight percent. Morepreferably, from about 20 to about 50 weight percent.

The second composition can be most readily made by melt mixing the fifthand sixth polymers in an apparatus such as a single or twin screwextruder that imparts sufficient shear to the mixture to disperse thefifth polymer in the sixth polymer. It is believed that this dispersiontakes place in many instances relatively easily compared to making othersimilar polymer blends because the fifth polymer (whether or not itcontains deliberately introduced reactive functional groups) reacts withmany of the sixth polymers which may be used, for example by opening ofsome of the lactone rings.

All of the compositions herein may additionally comprise other materialscommonly found in thermoplastic compositions, such as fillers,reinforcing agents, dyes, pigments, antioxidants, and antiozonants.These materials may be present in conventional amounts, which varyaccording to the type(s) of material(s) being added and their purpose inbeing added.

EXAMPLES

In the Examples the following abbreviations are used:

AIBN—azobis(isobutyronitrile)

n-BA—n-butyl acrylate

DAM—dry as made

DMA—dynamic mechanical analysis

DMAC—N,N-dimethylacetamideDMSO-dimethylsulfoxide

E—elongation

E′—storage modulus

F.M.—flexural modulus

GBL—γ-butyrolactone

GPC—gel permeation chromatography

HDT—heat deflection temperature

HEMA—2-hydroxyethyl methacrylate

LCP—liquid crystalline polymer

MBL—α-methylenebutyrolactone

MMA—methyl methacrylate

Mn—number average molecular weight

Mw—weight average molecular weight

NMP—N-methylpyrrolidone

PBT—poly(butylene terephthalate)

PET—poly(ethylene terephthalate)

POM—polyoxymethylene(polyacetal)

SAN—styrene/acrylonitrile copolymer

TEM—transmission electron microscopy

Tg—glass transition temperature

T.S.—tensile strength

MMA and AIBN were obtained from Aldrich Chemical Co., Milwaukee, Wis.,U.S.A. Paraloid® EXL-3361 and BTA 730L were obtained from Rohm & HaasCo., Philadelphia, Pa., U.S.A. γ-Butyrolactone (GBL) for thepolymerization solvent was obtained from Spectrum Chemical Co., NewBrunswick, N.J., U.S.A. Polyoxymethylene (POM, molecular weight 65,000),polybutylene terephthalate (PBT), I.V.=1.2), polyethylene terephthalate(PET, I.V.=0.65), liquid crystalline polyester (LCP, melt viscosity 52Pa·s@350° C.@1000 s⁻¹) and nylon 6,6 (molecular weight 16,500) wereobtained from E. I. DuPont de Nemours & Co., Inc., Wilmington, Del.,U.S.A. Styrene acrylonitrile (SAN, melt flow (230° C./3.8 kg)-8.7 g/10min) was obtained from Dow Chemical Co, Midland, Mich., U.S.A. Nylon 6(molecular weight 20,600) was obtained from Allied Signal, Morristown,N.J., U.S.A. Polycarbonate (melt flow @300° C./1.2 kg, ASTM D1238 is 3.5g/10 min) was obtained from GE Plastics, Pittsfield, Mass., U.S.A. TheNotched Izod testing was carried out according to ASTM D256 on specimensabout 3.2 mm thick. Haze and transmission were measured according toASTM D1003. Molecular weight was determined by triple detector GPC with2 Showdex® 80M columns, a Waters® 410 RI detector and a Viscotek® T60Alight scattering and viscometry detector. The solvent washexafluoroisopropanol and 0.01 M sodium triflate as the solvent andusing Zytel® 101 as a standard. Blending in a Brabender® mixer was donein a Brabender® Electronic Plasticorder®, Model EPL-5502 0236/SE from C.W. Brabender Instruments, S. Hackensack, N.J., U.S.A.

For Examples 12 to 22 melt mixing was carried out with a 16 mm twinscrew extruder, Welding Engineers Model TSE 16TC with a 3.2 mm die and60 kPa of vacuum on port no. 3, and was operated at 150 rpm. The screwhad three sets of partial conveying kneading blocks without reverseelements. Alternatively a twin screw extruder, model ZSK-30 manufacturedby Werner-Pfleiderer was used utilizing a screw having two kneadingblocks followed by a reverse element.

Glass transition temperatures were measured by ASTM D3418 at a heatingrate of 20° C./min and the Tg is taken as the midpoint of thetransition.

The flexural modulus was measured by ASTM D790.

The Tensile strength and % elongation was measured according to ASTMD638.

Heat deflection temperature was determined according to ASTM D648 at1.82 MPa load.

TEM was carried by sectioning molded plaques or pieces bycryo-ultramicrotomy. Sections of a nominal thickness 90 nm wereaccumulated in cold ethanol, transferred to water and retrieved oncopper mesh grids. For blends containing SAN, PBT or PET, the grids wereexposed to RuO₄ vapor for 2 h. Samples with Nylon were stained overnightby floating the sections on 1% aqueous phosphotungstic acid (PTA). POMblends were not stained but the sections were coated with carbon in avacuum evaporator to improve beam stability. Images were obtained usinga JEOL 1200 EX TEM operated at 100 KV accelerating voltage and recordedon sheet film. DMA measurements were performed by ASTM Method 4065 witha torque force of 1.2-1.4 N m. The bar was scanned in 3 Hz at 3° C./minrate from 140° C. to 220° C. The oscillation amplitude was 10 μm.

Experiment 1 Preparation of MBL Homopolymer

A solution of 200 g of MBL, 1 g AIBN and 1080 μL of ethyl acrylate and1250 μL of lauryl mercaptan was sparged with N₂ for 5 min. The solutionwas heated in a sealed polymerization tube at 60° C. for 6 h. The tubewas cooled and DMSO was added to dissolve the polymer. The DMSO solutionwas added dropwise to methanol and the polymer precipitate was collectedon a filter. The polymer was extracted with hot water in a Soxhletapparatus for 8 h and dried in a vacuum oven at 150° C. overnight. TheTg was 187° C.

Experiment 2 Preparation of MBL/MMA (70/30) Copolymer

A 500 ml feed flask was charged with 700 g of GBL solvent, 210 g MBL, 90g MMA and 1.5 g lauryl mercaptan. This mixture (150 ml) was added to a 2L jacketed reactor and was heated to 60° C. with a circulating waterbath. AIBN (1.5 g) was charged and the mixture was stirred for 15 min.The monomer/solvent/mercaptan mix was metered in slowly at a rate of 5g/h. After the addition was complete (157 min), the reaction was stirredfor 1 h and the temperature was then raised to 90° C. and continuedheating for 2 more h. The reaction mixture was cooled and slowly addedto 2.5 L of methanol under fast high shear stirring. The polymer powderwas collected on a Buchner filter funnel and dried in a vacuum oven at210° C. for 3 d. The Mn was 31,600, with a Mw/Mn of 2.00. The polymerhas a Tg of 145° C.

Experiment 3 Preparation of MBL/HEMA (95/5) Copolymer

A 1000 mL 3-necked flask equipped with a mechanical stirrer, refluxcondenser, and rubber stopper was charged with 250 mL NMP and heated to90° C. A mixture of MBL (95 g, 0.97 mol), 2-hydroxyethyl methacrylate (5g, 0.038 mol) and AIBN (100 mg, 0.61 mmol) was added dropwise over 4 h(via mechanical pump) while maintaining the temperature at 80° C. Aftercomplete addition, the temperature was raised to 115° C. and held for 3h. The viscous mixture was then diluted with 200 mL DMAC andprecipitated dropwise into 4500 mL of methanol. The white polymerprecipitate was collected via filtration, washed with water, and driedin a vacuum oven at 150° C. overnight. Yield 85 g (85%). Molecularweight by GPC was Mn 91,300, Mw/Mn was 11.2. Tg 175° C. (by DSC, N₂, 20°C./min.).

Control 1 Homopolymer of MBL

We have been unable to obtain a Notched Izod result for the poly-MBL onsamples made by compression molding because they crack in the upontaking samples out of the molds after compression molding.

Control 2 Homopolymer of MBL

Samples of completely transparent polyMBL (bulk polymerized using a cellcasting process, Mn of 126,500, Mw/Mn was 2.07) was cut with a lasercutter and had a Notched Izod of 11.7 Nm/m.

Example 1

MBL homopolymer (25 g) and a particle toughener with an acrylic core(Paraloid® 3361, 25 g) were mixed in a Brabender® apparatus at 250° C.,at 100 rpm under nitrogen for 5 min. Samples for impact testing werecompression molded at 250° C., at 276 MPa with a 15 ml pre-heat and 10ml press time. A plaque molded at 250° C., at 276 MPa, with a 15 minpreheat and 10 min press time was obtained which was visually nottransparent. The result for the Notched Izod was 28.8 Nm/m.

Example 2

MBL homopolymer (Experiment 1, 25 g) and a particle toughener with abutadiene/styrene core (Paraloid® BTA 730 L, 25 g) were mixed in aBrabender® mixer at 250° C. at 60 rpm under nitrogen for 5 min. Samplesfor impact testing were compression molded at 250° C., at 241 MPa, witha 10 min pre-heat and 10 min press time. The notched Izod was 10.7 Nm/m.The sample was slightly yellow and somewhat transparent. Haze was 57.1%,transmission 73.9%. The Tg after toughening was 190° C.

Example 3

MBL homopolymer (prepared similar to Experiment 2, 25 g) and a particletoughener with an acrylic core (Paraloid® KM 334, 25 g) were mixed in aBrabender® mixer at 250° C. at 100 rpm under nitrogen for 10 min.Samples for impact testing were compression molded at 250° C., at 241MPa, with a 10 min pre-heat and 5 min press time. The notched Izod was82.2 Nm/m. The sample was completely non-transparent.

Example 4

MBL homopolymer (prepared similar to Experiment 2, 25 g) and a particletoughener with an acrylic core (Paraloid® KM 365, 25 g) were mixed in aBrabender® mixer at 250° C. at 100 rpm under nitrogen for 10 min.Samples for impact testing were compression molded at 250° C., at 241MPa, with a 10 min pre-heat and 5 min press time. The notched Izod was107.3 Nm/m. The sample was completely non-transparent.

Example 5

MBL homopolymer (prepared similar to Experiment 1, 25 g) and a particletoughener with a 1,3-butadiene/styrene core (Paraloid® BTA 730L, 25 g)were mixed in a Brabender® mixer at 250° C. at 100 rpm under nitrogenfor 10 min. Samples for impact testing were compression molded at 250°C., at 241 MPa, with a 10 min pre-heat and 5 min press time. The notchedIzod was 55.0 Nm/m. The sample was yellow and somewhat transparent. Hazewas 66.9%, transmission 74.5%.

Example 6

A copolymer (90/10 MBL/MMA made in a similar fashion to Experiment 2, 40g) and Paraloid® BTA 730L (10 g) were mixed in a Brabender® mixer at220° C. and 100 rpm under nitrogen for 6 min. Samples for impact testingwere compression molded at 220° C., at 241 MPa, with a 10 min pre-heatand 2 min press time. The notched Izod was 35.8 Nm/m.

Example 7

A copolymer (60/40 MBL/MMA, made in a similar fashion to Experiment 2,40 g) and 10 g of Paraloid® BTA 730L were mixed in a Brabender® mixer at220° C. and 100 rpm under nitrogen for 6 min. Samples for impact testingwere compression molded at 220° C., at 241 MPa, with a 10 min pre-heatand 2 min press time. The notched Izod was 38.4 Nm/m.

Example 8

A copolymer (70/30 MBL/MMA as made in Experiment 2, 190 g) and Paraloid®BTA 730L (190 g) were mixed in a 16 mm twin screw extruder, WeldingEngineers Model TSE 16TC, at 230° C. with a throughput of about 1.4kg/h. The polymer strand was air cooled and pelletized. The Tg hadincreased slightly to 166° C. Samples for impact testing werecompression molded at 220° C., at 241 MPa, with a 10 min preheat and 2min press time. The sample was slightly yellow and somewhat transparent(haze=80.0%, transmission 82.8%). The notched Izod was 58.2 Nm/m.

Control 3 and Example 9

An ethylene/28 wt % n-butyl acrylate/5.25 wt % glycidyl methacrylate(EBAGMA) copolymer with an MBL-based resin were mixed for 5 min using aHaake® mixer at a set temperature of 210° C. and 100 rpm for 5 min.Results are given in Table 2.

Examples 10-11

The EBAGMA copolymer was blended with an MBL copolymer as made inExperiment 3 using a Brabender® mixer with a set temperature of 230° C.at 100 rpm for 5 min. Samples for impact testing were compression moldedat 230° C. at 241 MPa, with a 10 min pre-heat and 2 min press time. Bothsamples were not transparent. Results are given in Table 2.

TABLE 2 Example Example Control 3 Example 9 10 11 Material (wt. %)EBAGMA 19.8 19.8 10.0 30.0 MBL homopolymer 80.0 0 0 0 MBL/10 wt %MAA^(a) 0 80.0 0 0 MBL/5 wt % HEMA^(b) 0 0 90.0 70.0 Irganox ® 1010 0.20.2 0.0 0.0 Notched Izod, Nm/m 16.0 42.7 98.8 41.1 ^(a)Polymer was madein a fashion similar to Experiment 2. ^(b)See Experiment 3.

Experiment 4 Preparation of MBL/MMA (70/30) Copolymer

A 2 L feed flask was charged with 700 g of GBL solvent, 210 g MBL, 90 gMMA and 1.5 g lauryl mercaptan. Part of this mixture (150 ml) was addedto a 2 L jacketed reactor and was heated to 60° C. with a circulatingwater bath. AIBN (1.5 g) was charged and the mixture was stirred for 15min. The monomer/solvent/mercaptan mix was metered in slowly at a rateof 5 g/min. After the addition was complete (157 min), the reaction wasstirred for 1 h and the temperature was then raised to 90° C. andcontinued heating for 2 more h. The reaction mixture was cooled andslowly added to 2.5 L of methanol under fast high shear stirring. Thepolymer powder was collected on a Buchner filter funnel and dried in avacuum oven at 210° C. for 3 d. The Mn was 31,600, with a Mw/Mn of 2.00.The polymer has a Tg of 145° C.

Experiment 5 Synthesis of MBL Homopolymer

A 2 L feed flask was charged with 1140 g MBL, 60 g n-butyl acrylate, 6 gof AIBN and 6 g lauryl mercaptan. A 5 L jacketed reactor containing 3378g of butyrolactone was heated to with a circulating water bath to 84° C.The monomer/initiator/mercaptan mix was metered in slowly at a rate of6.7 g/min. After the addition was complete (207 min), the reaction wasstirred for 2 h. The reaction mixture was cooled and slowly added to 14L of methanol under fast high shear stirring. The polymer powder wascollected on a Buchner filter funnel and dried in a vacuum oven at 210°C. for 4 d. The Mn was 118,100, with a Mw/Mn of 1.61.

Examples 12-18 MBL/MMA (70/30)polymer Blends with 16 mm Extruder

The MBL/MMA copolymer of Experiment 4 was ground to a fine powder andmixed in a 20:80 weight ratio with 8 different matrix resins (eachground to a powder and dried in a vacuum oven). A 16 mm extruder washeated to 200° C. and each of the matrix resins were extruded followedby 0.45 kg. of the MBL powder blend. Table 3 shows the order in whichthe polymers were extruded, the feed rate and the temperature of thelast two zones of the extruder, as well as the Tg and particle size ofthe dispersed MBL copolymer. The polymer strand was quenched in waterand pelletized.

TABLE 3 Tg (° C.) Feed rate Barrel Temp ASTM Particle Size, μm Ex. Resin(kg/hr) (° C.) D3418 TEM 12 POM 1.4-1.8 200 — Up to 7x22 13 SAN 1.8-2.3230 106 0.07-3   14 PBT 1.6-2.7 250 — 0.14-3.7  15 Nylon 6 2.3 240  520.03-3.9  16 PET 1.8-2.3 270  85 0.17-1.7  17 LCP 1.6-2.7 270 — 0.5-5  18 nylon-6,6 1.8-2.5 270 — 0.7x0.7

Examples 25-31 MBL Polymer Blends with 30 mm Extruder

Several batches of MBL containing polymers were prepared similar toExperiments 4 and 5 were combined: 2000 g of MBL hompolymer, 600 g of a70/30 copolymer of MBL and MMA, and 1000 g of a 50/50 copolymer of MBLand MMA. Each of these polymers also had 2 wt % ethyl acrylate. Thecombined polymer sample was added to the rear of a 30 mm co-rotatingtwin screw extruder with intermeshing screws. The screw design used twosets of kneading blocks followed by reverse elements for two workingzones. The average composition of the MBL polymer was 70% MBL, 30% MMAwith Tg=164° C. This powder was co-fed in the extruder with threedifferent matrix resins: POM, PBT, and nylon 6,6. The feed rates wereadjusted so that a final blend of 40% MBL polymer with the matrixresins. The barrels were set to 210° C. for the POM, 240° C. for thePBT, and 290° C. for the nylon 6,6, the POM was run at 200 rpm and 9.1kg per hour, the PBT at 300 rpm and 9.1 kg per hour, and the nylon at300 rpm and 13.6 kg per hour. The blends and controls (no MBL copolymer)were molded on a 170 g (6 oz) Van Dorn reciprocating screw injectionmolding machine using a 90° C. mold temperature and a 25 sec screwretraction/25 sec screw forward time cycle at maximum pressure withoutflashing the mold. The mold had one 3.2 mm (thick) tensile bar and two3.2 mm flex bar cavities. The barrel settings were 190° C. for the POM,240° C. for the PBT, and 270° C. for the nylon 6,6. Results of thepolymer testing are given in Table 4.

TABLE 4 F.M. T.S. IZOD Particle size (TEM) DAM DAM % E DAM HDT Ex.MATRIX % μm GPa MPa DAM Nm/m ° C. Control 6 POM 100  2.55 68.9 47 389 9619 POM 70 0.14-5  3.21 60.0 5 206 112 Control 7 PBT 100  2.37 52.4 197239 52 20 PBT 60 0.1-8 3.50 51.7 3 163 102 21 PBT  60* 0.1-8 3.44 48.9 3156 103 Control 8 Nylon 6,6 100  2.90 82.7 36 267 72 22 Nylon 6,6 60 0.04-2.5 3.75 76.5 4 187 105 *0.05% Zn(OAc)₂ added.

Experiment 6 Preparation of MBL/n-butyl Acrylate Copolymer

A 500 mL 3 neck flask equipped with a mechanical stirrer, refluxcondenser, and rubber stopper was charged with 100 mL NMP and heated to90° C. A mixture of MBL (84 g), n-butyl acrylate (22 g), and AIBN (0.36g) was added dropwise over 2-3 h (via mechanical pump) while maintainingthe temperature at 90° C. After complete addition, the temperature wasraised to 110° C. and held for 3 h. The viscous mixture was then dilutedwith 250 mL NMP and precipitated dropwise into 1500 mL of methanol. Thewhite polymer precipitate was collected via filtration, washed withmethanol (Soxhlet extractor) and dried in a vacuum oven at 100° C.overnight. Yield 71 g (67%). Molecular weight; Mn 37,600, Mw 65,300, IV0.869 (HFIP); DSC; Tg 137° C.

Examples 23-24 Preparation of Poly-(MBL-co-n-butylacrylate)/polycarbonate Blends

The polymer prepared in Experiment 6 was blended with Lexan® 134polycarbonate in varying proportions (about 50 g total polymer) in aBrabender® mixer. Mixing conditions: RPM=50, set temperature=220° C.,melt temperature=228° C., torque=3000, mixing time=5 min. Properties ofthe blends are shown in Table 5.

TABLE 5 Polycarbonate/polyMBL- Tg Ex. co-nBA (by weight) Appearance (°C.) Control 9 100/0  Transparent 150 23 75/25 transparent, water 147white 24 50/50 transparent, water 143 white Control 10  0/100Transparent 137

Examples 25-31 MBL Polymer Blends with 16 mm Extruder

The MBL polymer of Experiment 5 was ground to a fine powder and mixed ina 20:80 weight ratio with 8 different matrix resins (each ground to apowder and dried in a vacuum oven). A 16 mm extruder was heated to 200°C. and each of the matrix resins were extruded followed by 0.45 kg. ofthe MBL powder blend. Table 6 shows the order in which the polymers wereextruded, the feed rate and the temperature of the last two zones of theextruder, as well as the Tg, storage modulus, E′, and particle size ofthe dispersed MBL copolymer. The polymer strand was quenched in waterand pelletized. Table 6 shows two characteristics of the 20% MBL blendswith a variety of polymers.

TABLE 6 Tg E′ @ Particle Size, Barrel (° C.) 25° C. μm Ex. Resin Feedrate (kg/hr) Temp (° C.) DMA (GPa) TEM 25 POM 1.4-1.8 200 −59 1.2 Up to6.5 26 SAN 1.8-2.3 230  98 1.5 0.07-6.5 27 PBT 1.6-2.7 250 54/189 2.00.14-10  28 Nylon 6 2.3 240 39/188 1.8 0.07-3.3 29 PET 1.8-2.3 28084/187 2.9 0.07-2.7 30 LCP 1.6-2.7 280 — — 0.2-3  31 nylon-6,6 1.8-2.5280 63/189 2.8 0.07-3.6

What is claimed is:
 1. A composition, comprising: (a) a first polymercomprising the repeat units: (i) at least about 10 mole percent of thetotal repeat units of

(ii) at least about 0.1 mole percent of a repeat unit containing a firstreactive functional group; (iii) up to about 89.9 mole percent of repeatunits derived from one or more monomers which are free radicallycopolymerizable with (a)(i) and (a)(ii); and (b) about 1 weight percentto about 50 weight percent based on the total weight of (a) and (b), ofa second polymer which is elastomeric and contains a second reactivefunctional group which may react with said first reactive functionalgroup; or (c) a third polymer comprising the repeat units (i) at leastabout 10 mole percent of the total repeat units of

(ii) up to about 90 mole percent of repeat units derived from one ormore monomers which are free radically copolymerizable with (b)(i); and(d) about 1 percent by weight to about 60 percent by weight based on thetotal weight of (c) and (d), of a fourth polymer which is core-shellparticles made up of an elastomeric polymer core and a polymericthermoplastic shell, said thermoplastic shell comprising repeat unitsderived from methyl methacrylate; wherein: n is 0, 1 or 2; X is —O— or—NR⁹—; and R¹, R², R⁵, R⁶, R⁹, each of R³, and each of R⁴, areindependently hydrogen, hydrocarbyl or substituted hydrocarbyl.
 2. Thecomposition as recited in claim 1 wherein R¹, R², R³, R⁴, R⁵ and R⁶ areall independently hydrogen or alkyl containing 1 to 6 carbon atoms, andX is oxygen.
 3. The composition as recited in claim 2 wherein n is
 0. 4.The composition as recited in claim 3 wherein R¹, R², R³, R⁴, R⁵ and R⁶are all hydrogen.
 5. The composition as recited in claim 4 wherein(a)(iii) or (c)(ii) are derived from one or more of

wherein R¹⁴ is hydrogen or methyl, R¹⁵ is hydrocarbyl or substitutedhydrocarbyl, and R¹⁶ is hydrogen or methyl, and R¹⁷, R¹⁸, R¹⁹, R²⁰ andR²¹ are each independently hydrogen, hydrocarbyl substituted hydrocarbylor a functional group.
 6. The composition as recited in claim 4 whichcomprises said first and said second polymers, wherein said first andsecond polymer contain one of an epoxy, carboxylic anhydride,isocyanato, hydroxyl, amino or carboxyl group.
 7. The composition asrecited in claim 6 wherein said first polymer contains about 0.1 toabout 25 mole percent of repeat unit (a)(ii), and said second polymercontains about 0.01 to about 1.5 moles of second reactive group per kgof said second polymer.
 8. The composition as recited in claim 6 whereinsaid second polymer is a copolymer of ethylene, an alkyl acrylate andglycidyl acrylate or methacrylate.
 9. The composition as recited inclaim 4 which comprises said third and fourth polymers, and said fourthpolymer is a core-shell polymer in which at least 50 mole percent of therepeat units in said shell are derived from methyl methacrylate.
 10. Thecomposition as recited in claim 9 wherein said core is elected from thegroup consisting of poly(1,3-butadiene-co-styrene) and an alkyl acrylatewherein said alkyl contains 2 to 4 carbon atoms.
 11. The composition asrecited in claim 4 which comprises said third and fourth polymers and istransparent, as measured by ASTM Method D1003.
 12. The composition asrecited in claim 1 wherein (a)(iii) or (c)(ii) are derived from one ormore of

wherein R¹⁴ is hydrogen or methyl, R¹⁵ is hydrocarbyl or substitutedhydrocarbyl, and R¹⁶ is hydrogen or methyl, and R¹⁷, R¹⁸, R¹⁹, R²⁰ andR²¹ are each independently hydrogen, hydrocarbyl substituted hydrocarbylor a functional group.
 13. The composition as recited in claim 1 wherein(a)(iii) or (c)(ii) are derived from methyl methacrylate and optionallyother copolymerizable monomers.
 14. The composition as recited in claim1 which comprises said first and said second polymers, wherein saidfirst and second polymers contain one of an epoxy, carboxylic anhydride,isocyanato, hydroxyl, amino or carboxyl group.
 15. The composition asrecited in claim 14 wherein said first polymer contains about 0.1 toabout 25 mole percent of repeat unit (a)(ii), and said second polymercontains about 0.01 to about 1.5 moles of second reactive group per kgof said second polymer.
 16. The composition as recited in claim 14wherein said second polymer is a copolymer of ethylene, an alkylacrylate and glycidyl acrylate or methacrylate.
 17. The composition asrecited in claim 1 which comprises said third and fourth polymers, andsaid fourth polymer is a core-shell polymer in which at least 50 molepercent of the repeat units in said shell are derived from methylmethacrylate.
 18. The composition as recited in claim 17 wherein saidcore is selected from the group consisting ofpoly(1,3-butadiene-co-styrene) and an alkyl acrylate wherein said alkylcontains 2 to 4 carbon atoms.
 19. The composition as recited in claim 1which comprises said third and fourth polymers and is transparent, asmeasured by ASTM Method D1003.